Amine acrylate addition reaction products

ABSTRACT

Amine acrylates are produced by the reaction of a diacrylate ester and an organic amine. The amine acrylates are rapidly cured by electron beam radiation as well as other types of radiation as well as by light curing means. These compounds and coating compositions containing them are highly useful in the field of protective coatings. Illustratively, the diacrylate ester of diethylene glycol is reacted with piperazine to produce piperazine diacrylate.

This application is a division of Ser. No. 69,136, filed on Sept. 2,1970, now U.S. 3,845,056, which was a continuation-in-part of Ser. No.6,939, filed on Jan. 29, 1970, now abandoned.

Many different coating compositions are known in the art and there is acontinuous effort to improve them. In the past many of these coatingscontained volatile solvents; however, recently compositions free of suchsolvents have been in demand to prevent air polution. Many such improvedcompositions have found commercial acceptance.

We have now found that certain amine acrylates and compositions thereofare readily cured by ultraviolet radiation, particulate or electron beamradiation or predominantly continuum light radiation. These amineacrylates can be used by themselves to produce protective coatings orthey can be mixed with other known coating compositions to enhance thecure rate of these other compositions. It has been found that the amineacrylates of this invention when used in coating compositions cure atextremely rapid rates.

The amine acrylates of this invention are produced by the reaction of apolyacrylate ester, preferably a diacrylate ester with an amine havingat least one hydrogen atom attached to the nitrogen atom. Thus, thesuitable amines can be the primary amines or the secondary amines;further, they can be monoamines or polyamines. The preferred amineacrylates are the amine diacrylate oligomers. However, polymeric typecompositions are also produced and obtained.

In its broader aspects the polyacrylate esters that can be used in theproduction of the amine polyacrylates are those having the structuralformula: ##EQU1## WHEREIN Y is the residue of a polyol (i.e. diol,triol, tetrol) used to produce the polyacrylate ester and r can be aninteger having a value of from 2 to 4 depending on whether the polyolwas a diol, triol or tetrol. For simplicity, the description will directitself mainly to those reactions using the diacrylate esters. However,this invention includes the triacrylate esters and the tetraacrylateesters. The amine acrylates produced with these higher functionalityesters are generally much more viscous, usually gel-like in nature, andfind preferred applications in the production of extruded shapedarticles, e.g., tubes, bars, rods, films, etc. In the production ofthese shaped articles these higher functional amine acrylates areextruded to shape and then cured by exposure to the radiation energy.

The suitable diacrylate esters for producing the amine acrylates havethe general structural formula: ##EQU2## wherein Z can be hydrogen ormethyl and R is the residue of the diol used to produce the diacrylateester as hereinafter described.

The production of esters, such as the diacrylate esters, is well knownto those of normal skill in the art. It is known that an acid such asacrylic acid or methacrylic acid will react with a dihydroxyl compoundor polyhydroxyl compound to produce the diester, or polyacrylate ester.In a simple illustration, acrylic acid reacts with ethylene glycol toproduce ethylene glycol diacrylate. The diacrylate esters can also beproduced by transesterification reactions. These reactions are known inthe art and the conditions under which they are carried out are so wellknown that they need not be set forth in detail.

The diols that are reacted with acrylic acid or methacrylic acid toproduce the diacrylate esters can be any of the compounds containing twohydroxyl groups that will undergo esterification. These are well knownand include the aliphatic-type diols having from two to about 20 carbonatoms, such as ethylene glycol, 1,2-propanediol, 1,3-propanediol,1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol,1,3,3-trimethyl-1,3-propanediol, 2-methyl-2-ethyl-1,3-propanediol,2-ethyl-1,3-hexanediol, 1,5-pentanediol, 1,10-decanediol, the5,6-dihydroxyalkylbicyclo[2.2.1]hept-2-enes having up to about fivecarbon atoms in the alkyl groups thereof, e.g.,5,6-dihydroxybicyclo[2.2.1]hept-2-ene,1-methyl-5,6-dihydroxyethylbicyclo[2.2.1]hept-2-ene,5,6-dihydroxymethylbicyclo[2.2.1]hept-2-ene,5,6-dihydroxyethylbicyclo[2.2.1]hept-2-ene,5-hydroxy-6-hydroxyethylbicyclo[2.2.1]hept-2-ene, the5,6-dihydroxypropylbicyclo[2.2.1]hept-2-enes,5-hydroxymethyl-6-hydroxybutylbicyclo[2.2.1]hept-2-ene, the5,6-dihydroxypentylbicyclo[2.2.1]hept-2-enes, the5,6-dihydroxyisopropylbicyclo[2.2.1]hept-2-enes,1,4-cyclohexanedimethanol, p-xylylene glycol, 4-hydroxybenzyl alcohol,1,4-cyclohexanediol; triols such as trimethylol propane, glycerol,1,2,6-hexanetriol; tetrols such as pentaerythritrol; and the like; theether glycols having a molecular weight of from about 106 to about15,000, including the heteric or block polyoxyalkylene diols, forexample, diethylene glycol, triethylene glycol, tetraethylene glycol,dipropylene glycol, tripropylene glycol, dibutylene glycol, thepolyethylene glycols and polypropylene glycols having from 2 to about350 oxyethylene or oxypropylene, respectively, groups in the molecule,the heteric and block poly(ethylene/propylene) glycols having from 2 toabout 350 oxyalkylene groups in the molecule, polytetrahydrofuran, andthe like; the ester glycols having at least one ester group and twohydroxyl groups in the molecule such as 2,2-dimethyl-3-hydroxypropyl2,2-dimethyl-3-hydroxypropionate, and the like; the caprolactone polyolsdisclosed in U.S. Pat. No. 3,169,945 that contain at least two hydroxylgroups and that have a molecular weight of from about 290 to about20,000, preferably from about 290 to about 2,000. The compounds namedand disclosed in U.S. Pat. No. 3,169,945 are incorporated herein byreference. Any dihydroxyl compound can be used that will react withacrylic acid or methacrylic acid to form an ester.

Hence, the residue of the diol used to produce the diacrylate ester,which residue is represented by R, can be a saturated or unsaturatedlinear or branched polyvalent alkylene wherein the saturated series isrepresented by the formula --C_(n) H_(2n) --wherein n is an integerhaving a value of from 2 to about 20 carbon atoms, those skilled in theart know the formulas of unsaturated series, which are preferablynon-conjugated; the unsubstituted or substituted divalentbicyclo[2.2.1]hept-5-ene group of the formula: ##SPC1##

wherein m is an integer having a value of 0 to 5; the unsubstituted orsubstituted divalent cycloalkylene group of the formula: ##SPC2##

the divalent aralkylene group of the formula: ##SPC3##

wherein p is from one to about 5 and x is zero or one; the divalentgroup of the formula:

    --C.sub.p H.sub.2p (OC.sub.p H.sub.2p).sub.y --

wherein y is 0 to about 350; the divalent group of the formula:

    --C.sub.p H.sub.2p (COOC.sub.p H.sub.2p).sub.y.sub.'   --

wherein y' is 1 to about 50; and the divalent group of the formula:

    --[(CH.sub.2).sub.5 COO].sub.z R' [OOC(CH.sub.2).sub.5 ].sub.z.sub.' --

wherein the sum of z plus z' is from 2 to an average total value ofabout 20 and R' is the residue of the organic functional initiator assaid term has been defined and its meaning established in U.S. Pat. No.3,169,945.

Illustrative of suitable diacrylate esters one can mention those listedin the following tabulation. In said tabulation the group attached to--R-- is specifically shown as the acrylyl group. However, it can alsobe the methacrylyl group; this has not been shown here in order to savespace and avoid repetition. The methacrylyl esters are obvious to oneskilled in organic chemistry. ##EQU3##

The amines reacted with the diacrylate ester compounds can be anyprimary or secondary amine, they can be monoamines or polyamines andthey can be aliphatic or aromatic, cyclic or acyclic. The suitableamines are those containing at least one reactive hydrogen atom attachedto the amine nitrogen atom. Illustrative thereof are the unsubstitutedand substituted amines of the following formulas: ##EQU4## wherein R" isa linear or branched alkyl having from 1 to about 10 carbon atoms,(R"'O)₃ SiC_(q) H_(2q) wherein R"' is alkyl of from 1 to 5 carbon atomsand q is an integer of from 1 to about 5, aryl or aralkyl or alkarylcontaining from 6 to about 12 carbon atoms, unsubstituted or substitutedcycloalkyl containing from 5 to about 10 carbn atoms; and X is adivalent oxygen atom, a divalent >NH group, a divalent >CR₂ "" groupwherein R"" can be hydrogen or alkyl of one to five carbon atoms, adivalent >NR'" group, or a divalent ##SPC4##

group in which m can be zero to 5.

Other suitable amines are the modified piperazine compounds. Theseinclude the reaction product of piperazine or alkyl substitutedpiperazines with mono-epoxides such as epichlorohydrin, styrene oxide,ethylene oxide, propylene oxide, butylene oxide, cyclohexane oxide, andthe like, or poly-epoxides such as diglycidyl ether of bisphenol A,4-vinyl-1-cyclohexene dioxide, and the like; the reaction product ofsaid piperazines with an isocyanate such as phenyl isocyanate, methylisocyanate, tolylene diisocyanate,bis(2-isocyanatoethyl)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylate,bis(2-isocyanatoethyl)4-cyclohexene-1,2-dicarboxylate, and the like. Inthese instances only one of the >NH groups of the piperazine compound isreacted and there is always an >NH group available from the piperazinemolecule. In illustration the product of the reaction of piperazine withstyrene oxide yields ##EQU5## and the product of the reaction with4-vinyl-1-cyclohexene dioxide yields ##SPC5##

Illustrative of useful amines one can mention methylamine, ethylamine,isopropylamine, n-butylamine, hexylamine, neoheptylamine,2-ethylhexylamine, decylamine, aminomethyltrimethoxysilane,aminoethyltriethoxysilane, aminoethyltributoxysilane,aminobutyltriethoxysilane, aminopentyltriethoxysilane, aniline,tolylamine, xylylamine, naphthylamine, benzylamine, phenethylamine,cyclopentylamine, methylcyclopentylamine, cyclohexylamine,dimethylcyclohexylamine, dimethylamine, dibutylamine, dioctylamine,N-methylamine, morpholine, piperazine, 2-methylpiperazine,N-methylpiperazine, N-propylpiperazine, piperidine, 2-ethylpiperidine,4,4'-dipiperidyl, 1,3-di(4-piperidyl)propane,1,5-di(4-piperidyl)pentane, and the like.

One can also use a polyamine such as ethylenediamine,diethylenetriamine, xylene diamine, hexamethylenetetramine,1,2-diaminopropane, 1,3-diaminopropane, imino-bis-propylamine, and thelike. In such instances one would produce a gel-like amine acrylatecompound that can be extruded or molded into a shaped article and thencured by radiation. While amine acrylates produced with polyamines havebeen made in the past, it has not previously been known or shown thatthey would rapidly cure to solid, cross-linked materials by theradiation procedures discussed herein.

The amine acrylates are produced by the reaction of a diacrylate esterof formula I with the amine. This reaction is preferably carried out inan inert gas atmosphere, for example, under nitrogen or argon, toprevent or minimize unwanted side reactions. However, this is notnecessary for a successful reaction.

The reaction can be carried out at a temperature of from about -30°C. orlower to about 150°C. or higher. The preferred temperature range is fromabout -10°C. to about 75°C. and the most preferred range is from about15°C. to about 40°C.

The pressure of the reaction system can be maintained at atmosphericpressure or superatmospheric pressure.

In the reaction, one of the acrylyl groups of the diacrylate esterreacts to displace the amino hydrogen atom while the second acrylylgroup of the diacrylate ester is not affected. This reaction can beshown by the following equation: ##EQU6## With piperazine the reactionis as follows: ##EQU7##

The molar amount of diacrylate ester charged to the reaction system canvary from about 0.9 mole to about 3 moles or more per amino hydrogenatom equivalent in the amino compound to produce the oligomers. Thepreferred amount of diacrylate ester is at least one mole thereof peramino hydrogen atom equivalent and it is common to use a slight excessof at least about 20 per cent. A low molecular weight polymer can beproduced by using a lower molar concentration of diacrylate ester; thiscan be as low as 0.55 mole thereof per amino hydrogen equivalent. Thisaspect is exemplified in Example 23.

The reaction can be carried out in the absence of a solvent or in thepresence of an inert solvent. Among the suitable inert organic solventsthat can be used one can mention methanol, ethanol, acetone, benzene,toluene, xylene, hexane, octane, and the like. Any inert solvent can beused that does not interfere with the reaction. In order to minimizeside reactions, the reaction is preferably carried out in the absence oflight.

In carrying out the reaction the diacrylate ester can be added to theamino compound or the amino compound can be added to the diacrylateester; the latter procedure is preferred. At the completion of thereacton, the amine acrylates are recovered as residue products; however,in some instances recovery by conventional distillation andfractionation procedures is possible. The amine acrylates can also beprepared by simultaneously spraying separate streams of the aminecompound and the diacrylate ester onto a surface or into an enclosedarea. In many instances the reaction is rapid and the two componentsquickly co-react. The means for simultaneously feeding two or moreseparate streams in the proper ratios are known in the art and suchequipment does not constitute a part of this invention.

Among the amine acrylates of this invention are those that can berepresented by the general formulas: ##EQU8## ##SPC6##

Illustrative of typical amine acrylates produced in this invention onecan mention those listed in Table B. In the left hand column of Table Bis shown the diacrylate ester from Table A that was used to produce theamine acrylate and in the right hand column there is shown the aminecompound that was used to produce the amine acrylate. The amineacrylates produced therefrom correspond to the compounds of Formulas Vto XI inclusive as indicated. Thus, when the diacrylate ester used wasCompound 1 of Table A and the amine compound was piperazine, the amineacrylate produced was ##EQU9## When the dimethacrylate ester of Compound14 of Table A is reacted with n-hexylamine, the amine acrylate is##EQU10## This preceding description will enable any chemist skilled inthe art to write out the chemical formula and understand the chemicalstructures and know the specific amine acrylate compounds set forth inTable B.

                  TABLE B                                                         ______________________________________                                        Amine Acrylates                                                               Diacrylate Ester                                                                         Amine            Amine Acrylate                                    From Table A                                                                             Compound         Formula Type                                      ______________________________________                                        Compound 1 CH.sub.3 NH.sub.2   V                                              Compound 8 CH.sub.3 NH.sub.2   V                                              Compound 22                                                                              CH.sub.3 NH.sub.2   V                                              Compound 18                                                                              CH.sub.6 H.sub.13 NH.sub.2                                                                        V                                              Compound 14                                                                              tolylamine          V                                              Compound 19                                                                              benzylamine         V                                              Compound 21                                                                              cyclohexylamine     V                                              Compound 22                                                                              (C.sub.2 H.sub.5 O).sub.3 SiC.sub.3 H.sub.6 NH.sub.2                                              V                                              Compound 14                                                                              (C.sub.4 H.sub.9 O).sub.3 SiC.sub.3 H.sub.6 NH.sub.2                                              V                                              Compound 6 C.sub.6 H.sub.13 NH.sub.2                                                                         VI                                             (1 mole)                                                                      Compound 14                                                                              (CH.sub.3).sub.2 NH VI                                             Compound 17                                                                              (C.sub.8 H.sub.17).sub.2 NH                                                                       VI                                             Compound 14                                                                              N-methylpiperazine  VI                                             Compound 3 piperazine          VII                                            Compound 8 piperazine          VII                                            Compound 11                                                                              piperazine          VII                                            Compound 22                                                                              piperazine          VII                                            Compound 26                                                                              piperazine          VII                                            Compound 14                                                                              2-methylpiperazine  VII                                            Compound 2 morpholine          VIII                                           Compound 7 morpholine          VIII                                           Compound 10                                                                              morpholine          VIII                                           Compound 21                                                                              morpholine          VIII                                           Compound 6 piperadine          IX                                             Compound 14                                                                              piperidine          IX                                             Compound 19                                                                              piperidine          IX                                             Compound 23                                                                              2-ethylpiperidine   IX                                             Compound 15                                                                              piperidine          IX                                             Compound 1 N-methylpiperazine  X                                              Compound 4 N-methylpiperazine  X                                              Compound 9 N-pentylpiperazine  X                                              Compound 14                                                                              N-isopropylpiperazine                                                                             X                                              Compound 18                                                                              N-ethylpiperazine   X                                              Compound 25                                                                              N-ethylpiperazine   X                                              Compound 6 4,4'-dipiperidyl    XI                                             Compound 11                                                                              4,4'-dipiperidyl    XI                                             Compound 24                                                                              4,4'-dipiperidyl    XI                                             Compound 6 1,3-di(4-piperidyl)propane                                                                        XI                                             Compound 8 1,3-di(4-piperidyl)propane                                                                        XI                                             Compound 19                                                                              1,5-di(4-piperidyl)pentane                                                                        XI                                             ______________________________________                                    

As previously indicated the amine acrylates are readily cured byultraviolet light radiation or electron beam radiation or high intensitypredominantly continuum light radiation. The curing is very rapid and adurable protective film is formed. One can also cure the compositions ina molded or extruded form to produce intricately shaped articles such asrods, tubes, films and the like.

The coating compositions can be applied to a surface by any of the knownconventional means, including the spray, curtain, dip, pad androll-coating techniques. The substrate to be coated can be anycomposition; for example, wood, metal, paper, plastic, fabric, fiber,ceramic, concrete, plaster, glass, etc.

The amine acrylate-containing compositions can be cured by ionizingradiation, either particulate or non-particulate, or non-ionizingradiation. As a suitable source of particulate radiation, one can useany source which emits electrons or charged nuclei. Particle radiationcan be generated from electron accelerators such as the Van de Graaff,resonance transformers, linear accelerators, insulating coretransformers, radioactive elements such as cobalt-60, strontium-90, etc.As a suitable source of non-particulate ionizing radiation, one can useany source which emits radiation in the range of from about 10⁻ ³Angstroms, to about 2000 Angstroms, preferably from about 5×10⁻ ³Angstroms to about 1 Angstrom. Suitable sources are vacuum ultravioletlamps, such as xenon or krypton arcs, mercury lamps, and radioactiveelements such as cesium-137, strontium-90 and cobalt-60. The nuclearreactors are also known to be a useful source of radiation. As asuitable source of non-ionizing radiation, one can use any source whichemits radiation of from about 2000 Angstroms to about 4500 Angstroms.Suitable sources are mercury arcs, carbon arcs, tungsten filament lamps,xenon arcs, krypton arcs, sunlamps, lasers, and the like. All of thesedevices and sources are well known in the art and those familiar withthe technology are fully aware of the manner in which the radiation isgenerated and the precautions to be exercised in its use.

The ionizing radiation dosage necessary to effect crosslinking will varydepending upon the particular polymer that is undergoing radiation, theextent of crosslinking desired, the number of crosslinkable sitesavailable and the molecular weight of the starting polymer. The totaldosage will be from about 10⁻ ³ rads to 10⁻ ⁸ rads, preferably from 5 ×10⁻ ³ rads to 10⁻ ⁷ rads. A rad is 100 ergs of ionizing energy absorbedper gram of material being irradiated.

The radiation is carried out at a temperature below the decompositiontemperature of the resin undergoing treatment, generally it isperferably from about -80° to about 125°C.

The use of low to high pressure mercury lamps to generate ultravioletlight is known. The largest such mercury lamp of commercial utility isgenerally about 5 feet long having a diameter of about 1 to 2 incheswith an electrical input of about 20 kilowatts generating a typical lowintensity ultraviolet light line structure (source intensity isgenerally no greater than about 20 kilowatts per square foot of sourceprojected area). An appreciable period of time is generally needed forcompletion of a reaction when a material is exposed to the low intensityultraviolet radiation generated from a mercury lamp.

It has been indicated that high intensity predominantly continuum lightradiation can also be used to cure or crosslink the amine acrylates orcompositions containing the amine acrylates.

Recently a source of light radiation emitting high intensitypredominantly continuum light radiation containing ultraviolet, visibleand infrared radiation that can be used to polymerize monomers and tocrosslink polymer compositions was discovered, namely the swirl-flowplasma arc radiation source. By means of proper light filters one canselectively screen out a portion of the light radiation emittedpermitting only that wavelength portion desired to reach the materialbeing treated.

The term "high intensity predominantly continuum light radiation" meanscontinuum radiation with a source intensity of at least 350 watts persquare centimeter steradian (about 1000 kilowatts per square foot)having only a minor part of the energy in peaks of bandwidths less than100 Angstrom units, with less than about 30 per cent of the lightradiated having wavelengths shorter than 4,000 Angstrom units and atleast about 70 per cent of the light energy radiated having wavelengthslonger than 4,000 Angstrom units.

This light radiation is derived from an artificial source that generateshigh intensity predominantly continuum light radiation with a sourceintensity of at least about 350 watts per square centimeter steradian,as abreviated by the term: watts cm⁻ ² sr⁻ ¹ ; said high intensitypredominantly continuum artificial light radiation has about 70 per centof the light radiated at a wavelength longer than 4,000 Angstroms andless than about 30 per cent of the light radiated having a wavelengthshorter than 4,000 Angstroms, generally about 80 per cent of the lightradiated has a wavelength longer than 4,000 Angstroms and less thanabout 20 per cent of the light radiated has a wavelength shorter than4,000 Angstroms, and a source intensity that can vary from about 350watts (about 1,000 kilowatts per square foot of source projected area)to about 5,000 watts (about 15,000 kilowatts per square foot of sourceprojected area) or more per square centimeter steradian. A convenientsource of high intensity predominantly continuum light radiation is aswirl-flow plasma arc light radiation apparatus. The equipment forgenerating high intensity predominantly continuum light radiation bythis means is known and available; many different forms thereof aredescribed in the literature. A highly efficient apparatus for obtaininghigh intensity predominantly continuum light radiation is the swirl-flowplasma arc radiation source described in U.S. Pat. No. 3,364,387. Theapparatus or equipment necessary for generating the light radiation isnot the subject of this invention and any source or apparatus capable ofgenerating high intensity predominantly continuum light radiation can beused.

While any artificial source of generating high intensity predominantlycontinuum light radiation can be used, as previously indicated theswirl-flow plasma arc radiation apparatus is most convenient. Hence,this source will be used in this application as illustrative of a meansfor obtaining the high intensity continuum light radiation. Anyapparatus that operates according to the known principles of theswirl-flow plasma arc radiation source can be used to produce the highintensity predominantly continuum light radiation useful in theprocesses of this invention. These apparatuses are often known by otherterms but those skilled in this art recognize that they emit highintensity predominantly continuum light radiation. The source ofradiation in a 50 kilowatt swirl-flow plasma arc radiation source is anarc only about four inches long enclosed in a quartz envelope about 1.5inches in diameter. This lamp can be readily removed and refurbished andhas an acceptable long lifetime. Further, a swirl-flow plasma arcradiation apparatus having a 250-kilowatt rating would be only about twoor three times as large as a 50-kilowatt source. Another advantage isthe absence of a need for expensive radiation shielding. Precautionsrequired for the artificial light sources include those needed toprotect one's eyes from the intense visible light and from theultraviolet light present to prevent inadvertent sunburn effect on thebody.

It is to be noted that in the spectra of high intensity predominantlycontinuum light radiation there is a continuum of radiation throughoutthe entire spectral range. This type of continuum radiation in theultraviolet range has not heretofore been obtainable from theconventional commercial mercury arcs or lamps generally available forgenerating ultraviolet light. The previously known means for generatingultraviolet light produced light that shows a line or peak spectrum inthe ultraviolet range, it is not a continuum spectrum in the ultravioletrange. In a line spectrum the major portion of useable ultraviolet lightis that portion at which the line or band in the spectrum forms a peak;in order for such energy to be useful the material or composition thatis to be treated with ultraviolet radiation must be capable of absorbingat that particular wavelength range at which the peak appears. In theevent the material or composition does not have the ability to absorb atthat particular wavelength range there is little or no absorption orreaction. Thus, in the event the material or composition to be treatedabsorbs at a particular wavelength range in one of the valleys of thespectral curve there will be little or no reaction since there is littleor no ultraviolet energy to adequately excite the system. With a highintensity predominantly continuum radiation, there is a high intensitycontinuum radiation of ultraviolet energy across the entire ultravioletwavelength range of the spectrum and there is generally sufficientultraviolet energy generated at all useful ultraviolet wavelengths toenable one to carry out reactions responsive to ultraviolet radiationwithout the problem of selecting compounds that will absorb at the peakwavelength bands only. With the high intensity continuum radiation nowdiscovered one does not have the problem of being unable to reactmaterials or compositions that absorb in the valley areas only since forall intents and purposes such valleys do not exist in high intensitycontinuum radiation, the high intensity radiated light energy isessentially a continuum, it is not in peak bands.

High intensity predominantly continuum light radiation is to bedistinguished from low intensity ultraviolet radiation generated bycommercially available low, medium and high pressure mercury arcultraviolet lamps. These mercury arc lamps produce light emission whichis primarily line or peak rather than continuum light, wherein a majorpart of the light appears in bands narrower than 100 Angstrom units, andmuch less than 70 per cent is above 4,000 Angstrom units.

As is known, high intensity predominantly continuum light radiation froma swirl-flow plasma arc radiation source is emitted from an arcgenerated between a pair of electrodes that are lined up axially andencased in a quartz cylinder. In an embodiment a pair of concentricquartz cylinders between which cooling water or gas flows is used. Arare gas, such as argon, krypton, neon or xenon, introduced into theinner cylinder tangentially through inlets located at one end of theinner cylinder, creates a swirling flow or vortex which restricts thearc to a small diameter. An electrical potential applied across theelectrodes causes a high density current to flow through the gas togenerate a plasma composed of electrons, positively charged ions andneutral atoms. A plasma generated in the above gases produces highintensity predominantly continuum light radiation with diffuse maxima inthe region of from about 3,500 to about 6,000 Angstroms. The radiationsource can also be used with reflectors or refractive optical systems todirect the high intensity predominantly continuum light radiationemanating from the arc to a particular point or direction or geometricalarea.

Crosslinking with the predominantly continuum light radiation from aswirl-flow plasma arc radiation source is usually carried out at ambienttemperature. The time necessary for curing the amine acrylate-containingcompositions will vary from a fraction of a second to 30 seconds ormore. In some instances as much as several minutes may be required if athick, pigmented layer is being cured. The necessary time for completionof curing is dependent upon the particular amine acrylate used as wellas any other component that may be present in the coating composition.

The rate of curing can be enhanced by the addition of suitablephotosensitizers. Illustrative of suitable photosensitizer compounds onecan mention acetophenone, propiophenone, benzophenone, xanthone,fluorenone, benzaldehyde, fluorene, anthraquinone, triphenylamine,carbazole, 3- or 4-methylacetophenone, 3- or 4pentylacetophenone, 3- or4-methylbenzophenone, 3- or 4-chlorobenzophenone,4,4'-bis(dimethylamino)benzophenone, 4,4'-dimethoxybenzophenone,4-chloro-4'-benzylbenzophenone, 3-chloroxanthone, 3,9-dichloroxanthone,3-chloro-8-nonylxanthone, 3-methoxyxanthone, 3-iodo-7-methoxyxanthone,and the like. As is obvious one can use a mixture of photosensitizers.The amount of photosensitizer used can vary from about 0.01 to about 20weight per cent of the coating solution. A preferred amount is fromabout 0.1 to about 5 weight per cent, and most preferred is aconcentration of from about 0.5 to about 3 weight per cent.

As previously indicated the amine acrylates, singly or in mixtures, canbe blended with from 1 to about 50 weight per cent or more of othercoating compositions that are known to cure on exposure to radiation.The concentration of amine acrylates blended into such compositions canvary from about 1 to 99.9 weight per cent of the coating composition,preferably from about 10 to about 75 weight per cent. These coatingcompositions can also contain from about 5 to about 50 weight per centof a polymerizable solvent such as styrene or a high boiling acrylylester.

The high boiling acrylyl esters that are useful in this invention cancontain more than one acrylyl group in the molecule; they are well knownin the art and can be represented by the general formula: ##EQU11##wherein Z can be hydrogen or methyl; r' is an integer having a value offrom 1 to about 4; and Y' can be Y or it can be a monovalent group suchas hydrogen; alkyl of from 1 to about 18 carbon atoms (e.g. methyl,ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, pentyl, hexyl,2-methylhexyl, 2,3-dimethylbutyl, neopentyl, heptyl, neohexyl,3,3-dimethylpentyl, octyl, 2-ethylhexyl, nonyl, decyl, etc.);alkoxyalkyl having up to about 15 carbon atoms (e.g. methoxymethyl,methoxybutyl, methoxydecyl, ethoxyethyl, ethoxyoctyl, butoxyethyl,butoxypropyl, hexoxyethyl, decoxyethyl, decoxypentyl, etc.); haloalkyl,wherein the alkyl group has up to about 15 carbon atoms as defined aboveand the halogen can be fluorine, chlorine, bromine or iodine (e.g.chloromethyl, chlorodecyl, fluoroethyl, bromoethyl, iodomethyl,dichloroethyl, perfluoroisopropyl, trichlorobutyl, etc.); cyano;cyanoalkyl wherein the alkyl group has up to about 15 carbon atoms asdefined above (e.g. cyanomethyl, cyanoethyl, cyanobutyl, cyanodecyl,etc.); epoxyalkyl wherein the alkyl group has up to about 15 carbonatoms as defined above (e.g. glycidyl, 4,5-epoxypentyl,2,3-epoxycyclohexyl, etc.); aryl (e.g. phenyl, xylyl, tolyl, naphthyl,naphthal, benzyl, etc.); aryloxyalkyl wherein the alkyl group has up toabout 15 carbon atoms as defined above (e.g. 2-phenoxyethyl,10-phenoxydecyl, 2-tolyloxyethyl, 2-naphthyloxyethyl, etc.);trialkoxysilyloxyalkyl wherein the alkoxy group has from 1 to about 5carbon atoms and the alkyl group has up to about 15 carbon atoms asdefined above (e.g. trimethoxysilyloxymethyl, trimethoxysilyloxypropyl,trimethoxysilyloxydecyl, triethoxysilyloxyethyl, triethoxysilyloxybutyl,tripropoxysilyloxyethyl, tributoxysilyloxyethyl, etc.); -CONG₂, whereinG can be hydrogen or hydrocarbyl having up to about 15 carbon atoms(e.g. N-methyl, N-ethyl, N-propyl, N-butyl, N-decyl, N,N-dimethyl,N,N-diethyl, N,N-diisobutyl, N-cyclohexyl, N,N-dicyclohexyl, N-phenyl,N-naphthyl, N-methyl-N-phenyl, N,N-diphenyl, N-benzyl, N,N-dibenzyl,N-tolyl, etc.); dicyclopentenyl; bicyclo[2.2.1]hept-2-en-5-yl;bicyclo[2.2.1]hept-2-en-5-yl; bicyclo[2.2.1]hept-2-en-5-yl-alkyl,wherein the alkyl group has from 1 to about 4 carbon atoms (e.g.bicyclo[2.2.1]hept-2-en-5-ylmethyl, bicyclo[2.2.1]hept-2-en-5-ylpropyl,etc.). As indicated Y' can also be Y; in such instances it is apolyvalent group such as a divalent --C_(p) H_(2p) --group wherein p hasa value of from 1 to about 10 (e.g. methylene, ethylene, propylene,isopropylene, butylene, hexylene, 2,2-dimethylbutylene, 2-ethylhexylene,decylene, etc.); --C_(r) H_(2r) (OC_(r) H_(2r))_(v) -- wherein r has avalue of from 2 to about 4 and v has a value of from about 1 to about5000 and the oxyalkylene portion thereof can be oxyethylene,oxypropylene, 2-oxypropylene, oxybutylene, or mixed oxyalkylene groupsin the same molecule, etc.; ##EQU12## a trivalent aliphatic hydrocarbonof the formula--C_(t) H_(2t) ₋₁ --wherein t has a value of from 3 toabout 10 (e.g. ##EQU13## or a tetravalent aliphatic hydrocarbon of theformula--C_(s) H_(2s) ₋₂ --wherein s has a value of from 4 to about 10(e.g. ##EQU14##

These high boiling acrylyl compounds are well known in the art and manyof them are described in "Vinyl and Related Polymers" by C. E.Schildknecht, published in 1952 by John Wiley and Sons. The commonknowledge of these compounds makes the specific naming thereof in thisapplication unnecessary in view of the extensive description set forthabove.

The coating compositions are produced by mixing the selected componentsthereof by conventional known methods. The blend can be heated, ifdesired, to facilitate mixing.

Coating compositions having the amine acrylate compound present, aloneor in admixture, can contain fillers, pigments and other additivesconventionally present in coating compositions. These additives are sowell known to those skilled in the art that they need no specificmention; nor is it necessary for an understanding of this invention torecite concentrations thereof. The same can be said of the knownradiation curable coating compositions that can be admixed with theamine acrylates to improve the curing and crosslinking properties.

The following examples serve to further describe this invention. Thestructures were confirmed by nuclear magnetic resonance spectrumanalysis.

EXAMPLE 1

There was charged to a reaction flask 53.5 grams of diethylene glycoldiacrylate and, while stirring, there was added in a dropwise manner at20°C. a solution of 8.6 grams of piperazine in 22 ml. of anhydrousmethanol. The reaction mixture was stirred for an additional hour at20°C. and the methanol was stripped off. There was recovered 60 grams ofa residue, which was a colorless liquid containing the amine acrylatehaving the following formula, as confirmed by nuclear magnetic resonancespectrum analysis. ##EQU15##

The amine acrylate was used to coat metal panels, and the coated panelswere exposed to different types of radiation. When exposed to betaradiation from a 300-kilovolt electron beam accelerator under a nitrogenatmosphere, the coating was cured to a smooth surface with a 0.5-megaraddose.

A mixture of this amine acrylate with 3 weight per cent of benzophenonecured in 3 seconds under a 550-watt medium-pressure mercury arc. Thissame mixture was completely cured in 0.5 second when exposed to thepredominantly continuum light radiation from a 50-kilowatt argonswirl-flow plasma arc radiation source.

EXAMPLE 2

In a manner similar to that described in Example 1, 32.2 grams ofdiethylene glycol diacrylate was reacted with 8.6 grams of piperazine in22 ml. of anhydrous methanol. There was recovered 42.4 grams of theliquid, colorless amine acrylate as a residue product after removal ofmethanol at reduced pressure.

The amine acrylate was blended with 3 weight per cent of benzophenoneand it was used to coat a steel panel. This coating cured in 0.2 secondsto a dry tack-free film when exposed to the predominantly continuumlight radiation from a 50-kilowatt argon swirl-flow plasma arc radiationsource. The coating was smooth and had good impact resistance.

EXAMPLE 3

In a manner similar to that described in Example 1, 212 grams ofneopentyl glycol diacrylate was reacted with 34.4 grams of piperazine in88 ml. of anhydrous methanol. After removing methanol under vacuum,there was recovered 244.1 grams of the liquid, colorless amine acrylatehaving the following structural formula: ##EQU16##

This amine acrylate was blended with 3 weight per cent of benzophenone,and the blend was applied as a coating to a steel panel. The coatingcured in 1.3 seconds on exposure to the predominantly continuum lightradiation from a 50-kilowatt argon swirl-flow plasma arc radiationsource. The coating was smooth and had good impact resistance.

EXAMPLE 4

In a manner similar to that described in Example 1, 21.2 grams ofneopentyl glycol diacrylate was reacted with a solution of 10.5 grams of1,3-di(4-piperidyl)propane in 25 ml. of anhydrous methanol. Afterremoval of methanol under vacuum, there was recovered 32.8 grams of theliquid, colorless amine acrylate of the following structural formula:##SPC7##

A portion of this amine acrylate was blended with 3 weight per cent ofbenzophenone and coated on a steel panel as a film. This coating curedin 0.8 seconds on exposure to the predominantly continuum lightradiation from 50-kilowatt argon swirl-flow plasma arc radiation source.The coating was smooth and had good impact properties.

EXAMPLE 5

To 42.4 grams of neopentyl glycol diacrylate there was added at 20°C.,in a dropwise manner, 10.1 grams of n-hexylamine. After the addition wascompleted, the mixture was stirred at 20°C. for 15 minutes, then heatedto 40°C. and stirred for an additional 2 hours. The amine acrylatesolution was a colorless mixture of the two products shown in thefollowing formulas: the individual components were present in a ratio of3 parts of A to 2 parts of B. ##EQU17##

A portion of this amine acrylates mixture was blended with 3 weight percent of benzophenone and coated on a steel panel. The coating cured in2.4 seconds on exposure to the predominantly continuum light radiationfrom a 50-kilowatt argon swirl-flow plasma arc radiation source. Thecoating had good impact properties.

When the neopentyl glycol diacrylate was replaced with ethylene glycoldiacrylate and the reaction carried out under the same conditions, therewas obtained a colorless liquid solution that was a mixture of the amineacrylates having the following structural formulas:

    (CH.sub.2 =CHCOOCH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OOCCH.sub.2 CH.sub.2).sub.2 NC.sub.6 H.sub.13 ##EQU18##

this solution cured to a tack-free film when treated in the same manneras the immediately preceding amine acrylates mixture.

EXAMPLE 6

In a manner similar to that described in Example 1, 25.44 grams ofneopentyl glycol diacrylate was reacted with 10 grams ofN-methylpiperazine. There was obtained a colorless solution of amineacrylate having the following structural formula: ##EQU19##

A portion of this amine acrylate was blended with 3 weight per cent ofbenzophenone and coated on steel panels. The coatings cured to tack-freefilms in 10 seconds on exposure to the predominantly continuum lightradiation from a 50-kilowatt argon swirl-flow plasma arc radiationsource.

A series of experiments was carried out to produce different amineacrylates. The procedure followed was similar to that described inExample 1. When the amine compound was a solid it was initiallydissolved in anhydrous methanol and slowly added to the stirreddiacrylate. When the amine was a liquid it was added in a dropwisemanner to the diacrylate. Methylamine was added as a 40 per cent aqueoussolution, and the water was subsequently removed by azeotropicdistillation with benzene. In all instances the reaction was carried outunder a nitrogen atmosphere and in an amber glass reactor or a reactorwrapped in aluminum foil for the exclusion of light. The concentrationsof the reactants and the amine acrylates produced are shown in thefollowing table. Also shown in this table are the properties of coatingon steel panels. These coatings were obtained by blending the amineacrylate with 3 weight per cent of benzophenone and coating a steelpanel. The coatings were cured by exposure to the predominantlycontinuum light radiation from a 50-kilowatt argon swirl-flow plasma arcradiation source.

    __________________________________________________________________________    Reactants                    Coating Properties                                                            Impact                                           Diacrylate  Amine      Cure Time                                                                           In-lb    Sward                                                                              Adhesion                           Ex                                                                              Name  Moles                                                                             Name   Moles                                                                             Seconds                                                                             Reverse                                                                            Front                                                                             Hardness                                                                           %    H.sub.2 O                                                                        EtOH                                                                              NaOH.sup.a                                                                        H.sub.2                                                                       SO.sub.4.sup.b     __________________________________________________________________________     7                                                                              NPGDA 1.5 Piperazine                                                                           1.0 1.3   165  165 4    100  10 10  0   0                   8                                                                              NPGDA 2.0 Methylamine                                                                          1.0 1.3   165  165 12   0    10 10  0   2                   9                                                                              NPGDA 1.5 Methylamine                                                                          1.0 0.6   165  165 4    0    10 10  0   2                  10                                                                              NPGDA 1.25                                                                              Methylamine                                                                          1.0 0.5   165  165 6    100  10 10  0   2                  11                                                                              NPGDA 2.0 APTS   1.0 2.1   165  165 6    100  10 10  0   1                  12                                                                              NPGDA 1.5 APTS   1.0 1.3   165  165 8    100  10 10  0   2                  13                                                                              NPGDA 1.25                                                                              APTS   1.0 1.2   165  165 6    100  10 10  0   2                  14                                                                              DEGDA 2.0 Methylamine                                                                          1.0 1.2   100  165 6    0     3 10  0   1                  15                                                                              DEGDA 1.5 Methylamine                                                                          1.0 0.6   165  165 6    100                                16                                                                              DMHP  2.0 Piperazine                                                                           1.0 2.0   165  165 0    100   7 0   0   1                  17                                                                              DEGCDA                                                                              2.0 Methylamine                                                                          1.0 2.3   165  165 10   100   3 10  0   1                  __________________________________________________________________________     .sup.a Twenty per cent solution at 25°C. for 24 hours.                 .sup.b Three per cent solution at 25°C. for 24 hours.                  NPGDA - Neopentyl glycol diacrylate                                           DEGDA - Diethylene glycol diacrylate                                          APTS - gamma-Aminopropyltriethoxysilane                                       DMHP - 2,2-Dimethyl-3-hydroxypropyl 2,2-dimethyl-3-hydroxy-propionate         DEGCDA - Compound 22, Table A  Sward Hardness was determined using the        procedure set forth on page 138 of the Paint Testing Manual published by     Gardner Laboratory, Inc., P.O. Box 5728, Bethesda, Md. The impact test     procedure is described on page 146 of the same manual. Adhesion was     determined by scribing the film with a sharp knife into 101/8 inch     squares, pressing scotch tape firmly against the test surface at a     45° angle to the square and pulling the tape away with one quick     motion. The per cent adhesion is then determined visually.

The amine acrylate produced in Example 7 has the structure shown inExample 3. The amine acrylate of Examples 8 to 10 has the structure:##EQU20##

The amine acrylate of Examples 11 to 13 has the structure: ##EQU21##

The amine acrylate of Examples 14 and 15 has the structure:

    (CH.sub.2 =CHCOOCH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OOCCH.sub.2 CH.sub.2).sub.2 NCH.sub.3

the amine acrylate of Example 16 has the structure: ##EQU22##

The amine acrylate of Example 17 has the structure: ##EQU23## whereinthe sum of z plus z' is an average total value of 3.7.

EXAMPLE 18

A reactor was charged with 3180 grams of neopentyl glycol diacrylate andthere was bubbled into the stirred diacrylate 310 grams of methylamineat a temperature of 20°C. The amine acrylate produced was a colorlessliquid having a Brookfield viscosity of 1175 cps. at 25°C. This amineacrylate is a mixture of compounds having the structural formula:##EQU24## wherein x has a value of from 1 to 4. Coatings on steel panelswith 3 weight per benzophenone and without benzophenone cured to dryfilms on exposure to the predominantly continuum light radiation from a50-kilowatt argon swirl-flow plasma arc light radiation source.

EXAMPLE 19

A. A resin was prepared by reacting 21.4 grams of a caprolactone polyol,which was the reaction product of one mole of trimethylolpropane withcaprolactone to an average molecular weight of about 535, with 15.5grams of 80/20 mixture of 2,4- and 2,6-tolylene diisocyanate and 13.9grams of 2-hydroxyethyl acrylate. The resin has the basic structuralformula: ##SPC8##

B. An amine acrylate was prepared in a manner similar to that describedin Example 1 by slowly adding 25 parts by weight of morpholine to 75parts by weight of neopentyl glycol diacrylate contained in an amberreactor in an inert atmosphere. The amine acrylate has the structure:##EQU25##

C. A solvent solution was prepared containing equal parts of2-ethylhexyl acrylate and 2-butoxyethyl acrylate.

A series of coating compositions was prepared containing differentamount of the resin (A), solvent solution (C) and amine acrylate (B).These coating compositions were blended with 3 weight per centbenzophenone and the coatings were applied to steel panels. The coatingswere cured by exposure to the predominantly continuum light radiationfrom a 50-kilowatt argon swirl-flow plasma arc radiation source toproduce dry films. The compositions of the coatings and the exposuretimes are tabulated below:

           A       C       B         Exposure                                            Resin   Solvent Amine Acrylate                                                                          to Cure                                                                              Sward                                 Coating                                                                              (Parts) Parts   (Parts)   (sec)  Hardness                              ______________________________________                                                             (Glass = 100)                                            (1)    50      45       5        10     6                                     (2)    50      40      10        8      4                                     (3)    50      35      15        5      4                                     (4)    50      30      20        4      4                                     (5)    50      25      25        3      2                                     ______________________________________                                    

EXAMPLE 20

A. A resin was prepared as described in Section (A) of Example 19. Thisresin had the same basic structure as set forth therein.

B. An amine acrylate was prepared as described in Section (B) of Example19, having the same basic structure as set forth therein.

A series of coating compositions was prepared, each containing 50 partsof Resin (A). Compositions (1) to (7) contained 10 parts of AmineAcrylate (B). Each composition contained 3 parts of benzophenone. Inaddition, each conposition contained polymerizable acrylate monomers asindicated in the table. The coating compositions were applied as 0.5 to0.7 mil wet films on steel panels and cured by radiation at a distanceof 3.5 inches with electrons from a 300-kilovolt electron beam; theywere also cured by exposure to the predominantly continuum lightradiation from a 50-kilowatt argon swirl-flow plasma arc radiationsource at a distance of two feet from the arc and at a distance of fourfeet from an 80-kilowatt argon swirl-flow plasma arc radiation source.

    ______________________________________                                                    Coating Compositions                                              No.         Parts of Polymerizable Acrylate                                   ______________________________________                                        (1)        17 parts 2-butoxyethyl acrylate                                               10 parts 2-ethoxyethyl acrylate                                               10 parts diethylene glycol diacrylate                              (2)        10 parts 2-ethoxyethyl acrylate                                               10 parts diethylene glycol diacrylate                                         17 parts 2-hydroxyethyl acrylate                                   (3)        17 parts 2-ethylhexyl acrylate                                                10 parts 2-ethoxyethyl acrylate                                               10 parts diethylene glycol diacrylate                              (4)        27 parts 2-ethoxyethyl acrylate                                               10 parts diethylene glycol diacrylate                              (5)        27 parts 2-ethoxyethyl acrylate                                               10 parts neopentyl glycol diacrylate                               (6)        32 parts 2-ethoxyethyl acrylate                                                5 parts diethylene glycol diacrylate                              (7)        32 parts 2-ethoxyethyl acrylate                                                5 parts neopentyl glycol diacrylate                               ______________________________________                                    

The coatings cured under the electron beam had the following properties;all were given an eight magarad dose.

    __________________________________________________________________________                      Reverse                                                     Coating                                                                             Extractables*                                                                        Sward                                                                              Impact                                                                             Chemical Resistance**                                  Comp. mg./sp. in.                                                                          Hardness                                                                           in.-lb.                                                                            1% H.sub.2 SO.sub.4                                                                50% C.sub.2 H.sub.5 OH                            __________________________________________________________________________    (1)   0.47   30   >165 9    8                                                 (2)   0.48   34    50  10   8                                                 (3)   0.55   30   >165 9    8                                                 (4)   0.45   32    50  9    8                                                 (5)   0.59   38    50  9    8                                                 (6)   0.71   32   >165 9    8                                                 (7)   0.47   34   >165 9    8                                                 __________________________________________________________________________      *Reflux extraction with 10 per cent ethanol for 24 hours                     **Scale of 10 used in all tables                                         

The coatings cured by exposure to the light radiation from the50-kilowatt argon swirl-flow plasma arc radiation source had thefollowing properties: All of the coatings showed a reverse impact valuegreater than 165 in.-lb.

    __________________________________________________________________________    Coating                                                                             Exposure                                                                           Extractables                                                                         Sward                                                                              Chemical Resistance                                    Comp. Sec. mg./sq. in                                                                           Hardness                                                                           1% H.sub.2 SO.sub.4                                                                50% C.sub.2 H.sub.5 OH                            __________________________________________________________________________    (1)   5    0.52   26   10    9                                                (2)   3    0.23   34    4    7                                                (3)   5    0.42   28   10    9                                                (4)   4    0.41   28   10   10                                                (5)   4    0.42   28   10   10                                                (6)   3    0.36   22   10   10                                                (7)   3    0.45   22   10    9                                                __________________________________________________________________________

The coatings cured by exposure to the light radiation from the80-kilowatt argon swirl-flow plasma arc radiation source had thefollowing properties. All of the coatings were exposed for 2.7 secondsand all showed a reverse impact value greater than 165 in.-lb.

    ______________________________________                                        Coating  Sward      Chemical Resistance                                       Comp.    Hardness   1% H.sub.2 SO.sub.4                                                                      50% C.sub.2 H.sub.5 OH                         ______________________________________                                        (1)      28          9         7                                              (2)      32          9         9                                              (3)      34          8         9                                              (4)      44         10         9                                              (5)      44          8         10                                             (6)      30         10         10                                             (7)      26         10         9                                              ______________________________________                                    

EXAMPLE 21

A series of ink formulations was prepared by blending different colorsof conventional ink pigments with an amine acrylate prepared asdescribed in Example 3. In these ink formulations 85 grams of the amineacrylate, 15 grams of ink pigment and 3 grams of benzophenone wereblended together in a pebble mill. The inks were applied to steel panelsand then cured by exposure to the predominantly continuum lightradiation from a 50-kilowatt argon swirl-flow plasma arc radiationsource. In all cases the printing inks had good impact properties andadhesion; they were hard and glossy and they did not smear. The resultsare tabulated below:

    __________________________________________________________________________    Pigment                                                                               Wt.                                                                              Cure Time                                                                           Impact.sup.a                                                                           Sward.sup.b                                         Name    %  Seconds                                                                             Reverse                                                                            Front                                                                             Hardness                                                                           Adhesion.sup.c                                                                      H.sub.2 O                                                                        EtOH                                                                              NaOH.sup.d                                                                        H.sub.2 SO.sub.4.sup.e        __________________________________________________________________________    Black   15 3.2   165  165 16   100    9 9   0   2                             Chrome Yellow                                                                         15 1.1   165  165 2    100   10 9   0   0                             Blue    15 1.3   165  165 6    100    5 2   0   0                             TiO.sub.2                                                                             15 5.5   165  165 2     90   10 6   0   0                             Red     15 3.6   165  165 12   100   10 9   0   3                             __________________________________________________________________________     .sup.a Gardner Impact Test.                                                   .sup.b Glass equals 100.                                                      .sup.c Scotch tape cross-hatch test.                                          .sup.d Twenty per cent solution at 25°C. for 24 hours.                 .sup.e Three per cent solution at 25°C. for 24 hours.             

What is claimed is:
 1. An amine acrylate addition reaction product of aprimary or secondary organic amine and a polyacrylate, said reactionproduct being selected from the group of: ##EQU26## wherein Z ishydrogen or methyl; R" is alkyl of from 1 to 5 carbon atoms, cycloalkylof from 5 to 10 carbon atoms, or aryl or aralkyl or alkaryl of from 6 to12 carbon atoms;R"" is hydrogen or alkyl of from 1 to 5 carbon atoms;and R is the residue of a diol of the group of saturated aliphatic diolshaving from 2 to 20 carbon atoms, bicyclo[2.2.1]hept-2-ene diols,cyclohexyl diols, phenyl and mono- and di- lower alkyl phenyl diols,polyalkylene ether diols having from 2 to 4 carbon atoms in the alkylenegroup and ester glycols having from 1 to an average of 17.5 estergroups; and x has a value of from 1 to
 4. 2. An amine acrylate asclaimed in claim 1 of the formula: ##EQU27##
 3. An amine acrylate asclaimed in claim 1 of the formula:

    (CH.sub.2 =CHCOOCH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OOCCH.sub.2 CH.sub.2).sub.2 NC.sub.6 H.sub.13

and ##EQU28##
 4. An amine acrylate as claimed in claim 1 of the formula:##EQU29##
 5. An amine acrylate as claimed in claim 1 of the formula:

    (CH.sub.2 =CHCOOCH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OOCCH.sub.2 CH.sub.2).sub.2 NCH.sub.3


6. an amine acrylate as claimed in claim 1 of the formula: ##EQU30##wherein the sum of z plus z' is an average total value of 3.7.
 7. Anamine acrylate as claimed in claim 1 of the formula: ##EQU31## wherein xhas a value of from 1 to 4.